Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/02—Ethene

Definitions

• Transition metal complexes of selected bidentate ligands containing both phosphorous and nitrogen groups which coordinate to certain early and late transition metals are active catalysts (sometimes in the presence of other compounds) for the polymerization of ethylene.
• Polyethylenes prepared by some of these catalysts under certain conditions are novel, being highly branched and apparently having exceptionally stiff polymer chains in solution.
• Polyethylenes are very important items of commerce, large quantities of various grades of these polymers being produced annually for a large number of uses, such as packaging films and moldings.
• There are many different methods for making such polymers including many used commercially, such as free radical polymerization to make low density polyethylene, and many so-called coordination catalysts such as Ziegler-Natta-type and metallocene-type catalysts .
• Each of these catalyst systems has its advantages and disadvantages, including cost of the polymerization and the particular structure of the polyethylene produced. Due to the importance of polyethylenes, new catalyst systems which are economical and/or produce new types of polyethylenes are constantly being sought .
• O98/40420 describes the use of certain late transition metal complexes of ligands containing phosphorous and nitrogen as ingredients in polymerization systems for olefins. Many of the ligands disclosed herein are different from those disclosed in this reference.
• W097/48735 generally describes the use of certain complexes of late transition metals are polymerizations catalysts for olefins .
• the ligands in these complexes are those which contain both phosphorous and nitrogen. None of the ligands described herein are specifically described in this reference.
• Linear polyethylene is reported (J. Brandrup, et al . , Ed., Polymer Handbook, 3 r Ed., John Wiley _ Sons, New York, 1989, p. VII/6) to have a Mark-Houwink constant ( ⁇ ) of about 0.6-0.7 in 1, 2 , 4-trichlorobezene at 135°C. No mention is made of any polyethylenes with higher Mark-Houwink constants .
• This invention concerns, a first process for the production of polyethylene, comprising the step of contacting, at a temperature of about -100°C to about +200°C, ethylene and an active polymerization catalyst based on a transition metal complex of a ligand containing both phosphorous and nitrogen groups, characterized in that said complex is a Ti, Cr, V, Zr, Hf or Ni complex of a ligand of the formula
• T is hydrocarbylene, substituted hydrocarbylene or -CR 9 R 10 -
• R is hydrogen, hydrocarbyl or substituted hydrocarbyl ;
• R and R 4 are each independently hydrocabyl or substituted hydrocarbyl, provided that a carbon atom bound to a nitrogen atom has at least two other carbon atoms bound to it;
• R and R are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl; R and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom bound to a phosphorous atom has at least two other carbon atoms bound to it;
• R 9 and R10 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl
• R and R are each independently hydrocarbyl or substituted hydrocarbyl
• R is hydrocarbyl or substituted hydrocarbyl; and provided that R and R taken together may form a ring.
• Also disclosed herein is a second process for the production of polyethylene, comprising the step of contacting, at a temperature of about -100°C to about +200°C, ethylene and an active polymerization catalyst based on a transition metal complex of a ligand containing both phosphorous and nitrogen groups, characterized in that said active polymerization catalyst comprises a compound of the formula
• a first compound W which is a neutral Lewis acid capable of abstracting X " and alkyl group or a hydride group from M to form WXJ (WR ) ⁇ or WH " and which is also capable of transferring an alkyl group or a hydride to M, provided that WX " is a weakly coordinating anion; or
• T is hydrocarbylene, substituted hydrocarbylene or -CR 9 R 10 -;
• R is hydrogen, hydrocarbyl or substituted hydrocarbyl ;
• R and R are each independently hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom bound to a nitrogen atom has at least two other carbon atoms bound to it ;
• R and R are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl
• R 7 and R8 are each independently hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom bound to a phosphorous atom has at least two other carbon atoms bound to it ;
• R and R are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl
• R and R are each independently hydrocarbyl or substituted hydrocarbyl
• R is hydrocarbyl or substituted hydrocarbyl ,- and provided that R and R taken together may form a ring.
• This invention also concerns a third process for the production of polyethylene, comprising the step of contacting, at a temperature of about -100°C to about +200°C, ethylene and an active polymerization catalyst based on a transition metal complex of a ligand containing both phosphorous and nitrogen groups, characterized in that said active polymerization catalyst comprises a compound selected from wherein:
• M is Ti, Cr, V, Zr, Hf or Ni; each X is an anion; n is an integer so that the total number of negative charges on said anion or anions is equal to the oxidation sate of M;
• T is hydrocarbylene, substituted hydrocarbylene or
• R is hydrogen, hydrocarbyl or substituted hydrocarbyl ;
• R and R are each independently hydrocabyl or substituted hydrocarbyl, provided that a carbon atom bound to a nitrogen atom has at least two other carbon atoms bound to it;
• R and R are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl
• R 7 and R8 are each independently hydrocarbyl or substituted hydrocarbyl, provided that a carbon atom bound to a phosphorous atom has at least two other carbon atoms bound to it;
• R 9 and R10 are each independently hydrogen, hydrocarbyl or substituted hydrocarbyl ,- R 11 and R are each independently hydrocarbyl or substituted hydrocarbyl;
• R is hydrocarbyl or substituted hydrocarbyl
• Z is hydride or alkyl or any other anionic ligand into which ethylene can insert
• Y is a neutral ligand capable of being displaced by ethylene or a vacant coordination site
• Q is a relatively non-coordinating anion
• P is a divalent polyethylene group containing one or more ethylene units
• Z is an end group and provided that R 2 and R9 taken together may form a
• This invention also concerns a homopolyethylene which has a Mark-Houwink constant of about 1.0 or more when measured in 1, 2 ,4-trichlorobenzene.
• DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A structure drawn such as (V) ,
• (V) simply means that the ligand in the square bracket is coordinated to the metal containing moiety, as indicated by the arrow. None is implied about what atoms in the ligand are coordinated to the metal .
• hydrocarbyl group is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms.
• substituted hydrocarbyl herein is meant a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of "substituted” are heteroaromatic rings.
• (inert) functional group herein is meant a group other than hydrocarbyl or substituted hydrocarbyl which is inert under the process conditions to which the compound containing the group is subjected.
• the functional groups also do not substantially interfere with any process described herein that the compound in which they are present may take part in. Examples of functional groups include halo (fluoro, chloro, bromo and iodo) , ether such as -OR
• R is hydrocarbyl or substituted hydrocarbyl.
• the functional group may be near a cobalt or iron atom, such as R 4 , R , R , R , R 13 and R ,17 the functional group should not coordinate to the metal atom more strongly than the groups in compounds containing R , R , R , R , R , and R which are shown as coordinating to the metal atom, that is they should not displace the desired coordinating group .
• alkyl aluminum compound a compound in which at least one alkyl group is bound to an aluminum atom.
• Other groups such as alkoxide, hydride, and halogen may also be bound to aluminum atoms in the compound.
• neutral Lewis base a compound, which is not an ion, which can act as a Lewis base.
• examples of such compounds include ethers, amines, sulfides, and organic nitriles.
• cationic Lewis acid is meant a cation which can act as a Lewis acid. Examples of such cations are sodium and silver cations.
• relatively noncoordinating (or weakly coordinating) anions are meant those anions as are generally referred to in the art in this manner, and the coordinating ability of such anions is known and has been discussed in the literature, see for instance W. Beck., et al . , Chem. Rev. , vol. 88 p. 1405-1421 (1988) , and S. H. Stares, Chem. Rev. , vol. 93, p. 927-942 (1993), both of which are hereby included by reference.
• Such anions are those formed from the aluminum compounds in the immediately preceding paragraph and XJ including R 9 3 A1X ⁇ , R 9 2 A1C1XN R 9 A1C1 2 XJ and "R 9 A10X ⁇ " , wherein R is alkyl.
• an empty coordination site is meant a potential coordination site that is not occupied by a ligand. Thus if an ethylene molecule is in the proximity of the empty coordination site, the ethylene molecule may coordinate to the metal atom.
• a ligand that may add to ethylene is meant a ligand coordinated to a metal atom into which an ethylene molecule (or a coordinated ethylene molecule) may insert to start or continue a polymerization. For instance, this may take the form of the reaction (wherein L is a ligand) :
• transition metals are Ti, Cr, V, and Ni, and Ni is especially preferred. It is believed that for the most part Ti, Cr, V and other early transition metals will give polyolefins with a "normal" amount of branching. For a discussion of "normal" branching in polyolefins see
• R is hydrocarbyl especially alkyl or alkyl or halogen substituted aryl, more especially alkyl containing 2 to 6 carbon atoms and 2, 6-dialkylphenyl;
• R 4 is hydrogen or alkyl, hydrogen especially when R is alkyl or halogen substituted aryl;
• R 7 and R 8 are independently saturated hydrocarbyl, especially alkyl or cycloalkyl containing 3 to 8 carbon atoms ;
• R 5 and R 6 are independently hydrogen or methyl, more preferably both hydrogen;
• R 13 is alkyl or halogen substituted aryl, especially
• R and R are each independently hydrocarbyl or substituted hydrocarbyl, especially hydrocarbyl in which the carbon atom bound to the phosphorous atom is bound to at least 2 other carbon atoms;
• T is -CHR 4 - wherein R 14 is hydrogen or alkyl containing 1 to 6 carbon atoms, T is -CR R -, or T is o-phenylene;
• R R 1 1 0 0 i is hydrogen and R2 taken together form a ring, especially a carbocyclic rriinngg.
• TThhee rriinngg ffoorrmmeedd bbyy RR aanndd R may be part of monocyclic ring system, or part of another type of ring sysstteemm,, ssuuceh as aa bbiiccyycclliicc rriinngg ssyysstteemm..
• PPrreeffeeirred groups when R and R 9 taken together form a ring are
• Bu is butyl
• Cy is cyclohexyl
• Ph is phenyl.
• the temperature at which the polymerization is carried out is about -100°C to about +200 °C, preferably about 0°C to about 150 °C, more preferably about 25°C to about 100 °C.
• the ethylene concentration at which the polymerization is carried out is not critical, atmospheric pressure to about 275 MPa being a suitable range for ethylene and propylene.
• the polymerization processes herein may be run in the presence of various liquids, particularly aprotic organic liquids.
• the catalyst system, ethylene, and polyethylene may be soluble or insoluble in these liquids, but obviously these liquids should not prevent the polymerization from occurring.
• Suitable liquids include alkanes, cycloalkanes, selected halogenated hydrocarbons, and aromatic hydrocarbons .
• Hydrocarbons are the preferred solvent .
• Specific useful solvents include hexane, toluene, benzene, chloroform, methylene chloride, 1, 2 , 4-trichorobenzene, p- xylene, and cyclohexane.
• the catalysts herein may be "heterogenized” by coating or otherwise attaching them to solid supports, such as silica or alumina.
• solid supports such as silica or alumina.
• an active catalyst species is formed by reaction with a compound such as an alkylaluminum compound
• a support on which the alkylaluminum compound is first coated or otherwise attached is contacted with the nickel compound precursor to form a catalyst system in which the active nickel catalyst is "attached" to the solid support .
• These supported catalysts may be used in polymerizations in organic liquids, as described in the immediately preceding paragraph. They may also be used in so-called gas phase polymerizations in which the ethylene being polymerized are added to the polymerization as a gas and no liquid supporting phase is present.
• transition metal containing polymerization catalysts including those disclosed herein, are especially useful in varying the branching in polyolefins made with them, see for instance WO96/23010, WO97/02298, WO98/30610 and WO98/30609, incorporated by reference herein for all purposes as if fully set forth.
• blends of distinct polymers may have advantageous properties compared to "single" polymers. For instance it is known that polymers with broad or bimodal molecular weight distributions may be melt processed (be shaped) more easily than narrower molecular weight distribution polymers. Similarly, thermoplastics such as crystalline polymers may often be toughened by blending with elastomeric polymers.
• the catalysts disclosed herein can be termed the first active polymerization catalyst.
• Monomers useful with these catalysts are those described (and also preferred) above .
• a second active polymerization catalyst (and optionally one or more others) is used in conjunction with the first active polymerization catalyst.
• the second active polymerization catalyst may be another late transition metal catalyst, for example as described in previously incorporated WO96/23010, WO97/02298, WO98/30610, WO98/30609 and W098/27124.
• Other useful types of catalysts may also be used for the second active polymerization catalyst. For instance so-called Ziegler-Natta and/or metallocene-type catalysts may also be used. These types of catalysts are well known in the polyolefin field, see for instance Angew. Chem., Int. Ed. Engl . , vol. 34, p.
• Suitable catalysts for the second polymerization catalyst also include metallocene-type catalysts, as described in US5324800 and EP-A-0129368 ; particularly advantageous are bridged bis-indenyl metallocenes, for instance as described in US5145819 and EP-A-0485823.
• Another class of suitable catalysts comprises the well-known constrained geometry catalysts, as described in EP-A-0416815, EP-A-0420436, EP-A-0671404 and EP-A-0643066 , and WO91/04257. Finally, the class of transition metal complexes described in W096/13529 can be used.
• the first olefin (s) [the monomer (s) polymerized by the first active polymerization catalyst] and second olefin (s) [the monomer (s) polymerized by the second active polymerization catalyst] are identical, and preferred olefins in such a process are the same as described immediately above .
• the first and/or second olefins may also be a single olefin or a mixture of olefins to make a copolymer. Again it is preferred that they be identical particularly in a process in which polymerization by the first and second active polymerization catalysts make polymer simultaneously.
• the first active polymerization catalyst may polymerize a monomer that may not be polymerized by said second active polymerization catalyst, and/or vice versa. In that instance two chemically distinct polymers may be produced. In another scenario two monomers would be present, with one polymerization catalyst producing a copolymer, and the other polymerization catalyst producing a homopolymer, or two copolymers may be produced which vary in the molar proportion or repeat units from the various monomers. Other analogous combinations will be evident to the artisan. In another variation of this process one of the polymerization catalysts makes an oligomer of an olefin, preferably ethylene, which oligomer has the formula
• R 70CH CH 2 , wherein R70 is n-alkyl, preferably with an even number of carbon atoms.
• the other polymerization catalyst in the process them (co) polymerizes this olefin, either by itself or preferably with at least one other olefin, preferably ethylene, to form a branched polyolefin.
• Preparation of the oligomer (which is sometimes called an ⁇ -olefin) by a second active polymerization-type of catalyst can be found in previously incorporated WO96/23010 and W099/02472.
• the first active polymerization catalyst is described in detail above.
• the second active polymerization catalyst may also meet the limitations of the first active polymerization catalyst, but must be chemically distinct. For instance, it may have a different transition metal present, and/or utilize a different type of ligand and/or the same type of ligand which differs in structure between the first and second active polymerization catalysts. In one preferred process, the ligand type and the metal are the same, but the ligands differ in their substituents .
• two active polymerization catalysts include systems in which a single polymerization catalyst is added together with another ligand, preferably the same type of ligand, which can displace the original ligand coordinated to the metal of the original active polymerization catalyst, to produce in situ two different polymerization catalysts.
• the molar ratio of the first active polymerization catalyst to the second active polymerization catalyst used will depend on the ratio of polymer from each catalyst desired, and the relative rate of polymerization of each catalyst under the process conditions. For instance, if one wanted to prepare a "toughened" thermoplastic polyethylene that contained 80% crystalline polyethylene and 20% rubbery polyethylene, and the rates of polymerization of the two catalysts were equal, then one would use a 4:1 molar ratio of the catalyst that gave crystalline polyethylene to the catalyst that gave rubbery polyethylene . More than two active polymerization catalysts may also be used if the desired product is to contain more than two different types of polymer.
• the polymers made by the first active polymerization catalyst and the second active polymerization catalyst may be made in sequence, i.e., a polymerization with one (either first or second) of the catalysts followed by a polymerization with the other catalyst, as by using two polymerization vessels in series. However it is preferred to carry out the polymerization using the first and second active polymerization catalysts in the same vessel (s) , i.e., simultaneously. This is possible because in most instances the first and second active polymerization catalysts are compatible with each other, and they produce their distinctive polymers in the other catalyst's presence. Any of the processes applicable to the individual catalysts may be used in this polymerization process with 2 or more catalysts, i.e., gas phase, liquid phase, continuous, etc.
• the polymers produced by this "mixed catalyst” process may vary in molecular weight and/or molecular weight distribution and/or melting point and/or level of crystallinity, and/or glass transition temperature and/or other factors.
• the polymers may differ in ratios of comonomers if the different polymerization catalysts polymerize the monomers present at different relative rates.
• the polymers produced are useful as molding and extrusion resins and in films as for packaging. They may have advantages such as improved melt processing, toughness and improved low temperature properties.
• Hydrogen may be used to lower the molecular weight of polyethylene produced in the first or second processes. It is preferred that the amount of hydrogen present be about 0.01 to about 50 mole percent of the ethylene present, preferably about 1 to about 20 mole percent. The relative concentrations of ethylene and hydrogen may be regulated by their partial pressures.
• homopolyethylenes produced herein have exceptionally high Mark-Houwink constants. Most homopolyethylenes have such constants in the range of about 0.5 to 0.75, depending on the particular solvent and temperature used, as well as the degree of branching in the polyethylene. It is believed that "Generally, 0.5 ⁇ 0.8 for flexible chains, 0.8 ⁇ l .0 for inherently stiff molecules ( e . g. cellulose derivatives, DNA) and 1. O ⁇ l .7 for highly extended chains ( e. g.
• the polyethylenes with high Mark-Houwink constants are especially useful as viscosity modifiers, and are also useful the uses outlined for highly branched polyethylenes in WO96/23010, which is hereby included by reference, such as bases for lubricating oils, and lubricating oil viscosity modifiers.
• These polymers may be made by polymerizing using catalysts such as lb, Ic and Id, more preferably lb, and especially using higher polymerization temperatures, such as temperatures above about 50°C, especially above about 70°C, with maximum polymerization temperatures as described above.
• catalysts such as lb, Ic and Id, more preferably lb
• higher polymerization temperatures such as temperatures above about 50°C, especially above about 70°C, with maximum polymerization temperatures as described above.
• abbreviations are used: - Mark-Houwink constant
• Mn number average molecular weight
• Mw weight average molecular weight
• PMAO-IP methylaluminoxane
• TCB 1,2,4-trichlorobenzene
• THF- tetrahydrofuran Tm - melting point Melting points were determined by DSC, using a heating rate of 10°C/min. The melting point was taken on the 2 nd heat, and the peak of the melting endotherm was taken as the melting point.
• Intrinsic viscosity was measured in TCB at a temperature of 135°C.
• Branching levels as measured by 1H and 13C NMR were determined as described in WO96/23010.
• NiBr 2 complexes of the compounds prepared in Examples 1- 10 were prepared by similar procedures.
• the synthesis of the complex (Id) -NiBr 2 is described below: Into a suspension of (DME)NiBr 2 (90 mg, 0.29 mmol) in 5 mL dichloromethane, a solution of (Id) (121 mg, 0.29 mmol) in 5 mL of dichloromethane was added. The mixture was stirred at RT overnight. The solution was passed through Celite® to remove any insoluble material , then concentrated under vacuum by removal of the majority of the solvent. Finally, a large excess of hexane was added to the solution to precipitate the complex.
• the purple complex was filtered, washed with hexane, and dried (85 mg, 46% yield) .
• the ligands complex with metal ion it isomerizes into imine form from the enamine form.
• the crystal structure agreed with the complex structure .
• Example 23 An evacuated 600 mL autoclave was charged with a solution of (Ib)-NiBr 2 (20 mg, 0.033 mmol) in 100 mL of chlorobenzene . The autoclave was heated to 70°C. To this solution was then added PMAO-IP (4.0 mL in toluene, 16.5 mmol) under 3.5 MPa of ethylene. The resulting mixture was stirred at 70°C under 3.5 MPa of ethylene for 7 h. Ethylene pressure was then vented and the reaction mixture quenched under air by the addition of 50 mL of isopropanol . The white powder was filtered, washed with methanol, and finally dried in vacuo (0.5 g ) .
• PMAO-IP 4.0 mL in toluene, 16.5 mmol
• the branching distribution was quantified by 13 C NMR. Branching per 1000 CH 2 : Total methyls (49.4), Methyl (22.3), Ethyl (9.3), Propyl (1.1), Butyl (3.0), Amyl (2.2), and >Hexyl (11.2).
• Example 24 An evacuated 600 mL autoclave was charged with a solution of (Ic)-NiBr 2 (20 mg, 0.033 mmol) in 100 mL of chlorobenzene. The autoclave was heated 70°C. To this solution was then added PMAO-IP (4.0 mL in toluene, 16.6 mmol) under 3.5 MPa of ethylene. The resulting mixture was stirred at 70°C under 3.5 MPa of ethylene for 7 h. Ethylene pressure was then vented and the reaction mixture quenched under air by the addition of 50 mL of isopropanol. The resulting slurry was stirred in a beaker with 100 mL methanol plus 10 mL concentrated HCl .
• Example 30 An evacuated 600 mL autoclave was charged with a solution of (If)-NiBr 2 (50 mg, 0.074 mmol) in 100 mL of chlorobenzene. The autoclave was heated to 70°C. To this solution was then added PMAO-IP (9.0 mL in toluene, 37.2 mmol) under 2.1 MPa of ethylene. The resulting mixture was stirred at 100°C under 2.1 MPa of ethylene for 4.1 h.
• Example 35 A 20 mL glass shaker-tube was charged with VC1 3 ' 3THF
• Example 38 A 20 mL glass shaker-tube was charged with VC1 3 ' 3THF
• Example 41 A 20 mL glass shaker-tube was charged with VC1 3 ' 3THF
• a catalyst stock solution of VC1 3 ' 3THF (7.47 mg, 0.02 mmol) and (Ig) (7.15 mg, 0.02 mmol) in 10 mL of dry chlorobenzene was prepared.
• the catalyst solution (1.0 mL) was withdrawn and diluted into 10 mL of dry chlorobenzene.
• the catalyst solution (containing 0.2 ⁇ mol catalyst) was charged into an addition cylinder under nitrogen.
• a cocatalyst solution of MMAO (1.15 mL, 1000 eq.) in 100 mL heptane was charged into an evacuated 600 mL autoclave under nitrogen. The autoclave was heated 70°C.
• a control polymerization was run with the same amount of VC1 3 " 3THF and MMAO but with no ligand. Following the same procedure as described in Example 43 but without addition of any ligand, a polymerization was run at 70 °C for 2.57 h. White polymer (0.44 g) was obtained.

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